New cyclic urea derivatives



United States Patent 2,887,485 NEW CYCLIC UREA'DERIVATIVES Robert S.Yost, Oreland, Pa., assignor to Rohm & Haas Company, Philadelphia, Pa.,a corporation of Delaware No Drawing. Application January6, 1956 SerialNo. 557,656

10 Claims. (Cl. 260-251) This invention is, concerned withN-(halogenoalkyl)- N,N-alkyleneureas and to methods of producing them.This application is a continuation-in-part of my copending applicationSerial No. 500,300, now Patent No. 2,840,- 566, filed April 8, 1955, anda continuation-in-part of my copending application Serial No. 533,510,filed September 9, 1955, now Patent No. 2,840,561.

The novel compounds of the present invention have the structure of thegeneral Formulal:

HN/ \NZX whereA is'an alkylene group having 2 to3 carbonatoms of whichat least two extend in a chain between the adjoined N atoms, Z is analkylene group having 2m 18 carbon atoms of which at least two extend ina chain between the N and X atoms, and X isa halogen selected from thegroup consisting of chlorine and bromine.

The compounds of Formula I may be madeby the reaction of thionyl halidesof the Formula- II' with a compound of Formula III:

( SOX (III) HN/ \NZOH where X, A, and; Z are as defined above. Thethionyl halide and the compound of Formula III may be used inapproximately equimolar amounts and the reaction is preferably effectedin a solution of the compound of Formula III, such as in chloroform.Preferably the thionyl halide is added gradually. For example, when thereaction involves a batch containing about two moles of a compoundofForrnula III, the thionylhalide may be added over a period of twohours. Reaction is preferably effected at a temperature of 30 to 110 C.Advantageously, it may be carriedout with the solvent-atreflux, in thecase of chloroform, refluxing occurringat a temperature of about 58 to66 C. After completion of the addition of the thionyl halide, thesolvent, such as the chloroform, may be gradually distilled whileintroducing tolueneuntil the temperature in the vesseltreaches about 105to 109 C. It is then refluxed for about 20 hours in the toluene. Theproduct of Formula I is usually soluble in the hot toluene which iscooled to about 5 to C. or lower to precipitate the compound of FormulaI. The precipitated product may then be filtered and, if desired, washedwith cold toluene. It is then airdried or dried under a vacuum at roomtemperature. Instead of chloroform, other solvents, such as carbontetrachloride and ethylene dichloride, may be used; and in place oftoluene, other non-polar solvents, such as benzene, xylene, or the likemay be used.

2,887,485 Patented May 19, 1959 "ice The compounds of Formula III may bemade in various ways described inU. S. Patent 2,727,019. For example, asthere disclosed, urea may be condensed with ahydroxyalkylaminoalkylamine, such as any one of the followmg;

V(J): HOCH (C H CH NHCH (CH CHgNI-I V( n HOCH(CH=CH CH NHCH (CH CH NH V(0) HOCH (C H CH NHCH CH NH V( p) HOCH (C H CHQNHCH CH CH NH V( q) HOCH(C H CH NHCH CH NH V:(T) C.HPCH2 CHr-C 3 Thev reaction with urea may beeffected by mixing one of the, above hydroxy-diamines with anapproximately equimolecular weight of urea and heating the mixture atsuflicient temperature to evolve ammonia. Generally, temperatures may bebetween 200 to 210 C. Usually the reaction runs in two temperatureranges, initialevolution of ammonia occurring at to C., and thecompletion of the evolution of ammonia being effected at temperatures of150 to 200 C.

The compounds, of the present invention are generally solids to viscousliquids depending primarily upon the size of the .alkylene sub-stituentZ. Those compounds of Formula I having fairly'high molecular'weight,especially those in which the group Z has 12 to 18 carbon atoms arehighly hydrophobic and, when applied to textiles, leather, and paper,impart water-repellency thereto and at the same time exert more or lesssoftening and lubricating action. They are useful components of shoepolishes'as well as other dressing or finishing material for paper,textiles, and: leather products in general. Any of the compounds ofFormula I may first be preliminarily condensed with aldehydes, andespecially formaldehyde, to form alkylolated, and especiallymethylolated, derivatives which react with cellulosic and proteinaceousmaterials, especially textile fabrics of cellulose including cotton,viscose rayon, cuprarnmonium cellulose rayon or cellulose derivativessuch as ethers and esters of cellulose, including ethyl cellulose,methyl cellulose,.hydroxyethyl cellulose, cellulose acetate, and casein,soyabean protein, alpha-protein, and so on. Instead of first reactingthe aldehyde with the compound of the invention, thealdehyde maybeapplied together with such compound or immediately before or after. Ineither system, completion of the condensation, to an infusible andinsoluble condition is effected by baking or curing at elevated tem- Thecompounds of Formula I are also useful for producing quaternary ammoniumcompounds in the manner described in my co-pending application SerialNo. 500,300 supra (2,840,566) and in my application entitled QuaternaryAmmonium Compounds, Serial No. 557,654, filed on even date herewith, nowPatent No. 2,840,546.

In the following examples, which are illustrative of the invention, theparts are by weight unless otherwise indicated:

Example 1 In a reaction vessel fitted with mechanical stirrer,thermometer, dropping funnel and reflux condenser are placed 260 partsof N-(B-hydroxyethyl)-N,N-ethyleneurea (obtained from the condensationof urea with the compound of Formula V(a) above) and 600 parts ofanhydrous chloroform. The mixture is heated to reflux and 238 parts ofpurified thionyl chloride is added dropwise over a period of two hours.Reflux is maintained by the heat of reaction for most of this period.The chloroform is then distilled out of the mixture while 348 parts ofanhydrous toluene is added at approximately the same rate at which thechloroform is distilled. Distillation is continued until the vaportemperature reaches 110 C. The mixture is refluxed for sixteen hours andthen is chilled in an ice bath. The product is precipitated and isfiltered, Washed with cold toluene, and dried at 60 C. to give 268 parts(a 90% yield) of N-(fi-chloroethyl)-N,N'-ethyleneurea, M.P. 81.5" to 82C. Another name for this compound is 1-(;3-chloroethyl)-imidazolidinone-Z. One recrystallization from toluene gives a colorless,crystalline product melting at 84.0 to 85.0 C.

Analysis.Calculated for C H ON C1: C, 40.41%; H, 6.11%; N, 18.86%; Cl,23.86%. Found: C, 40.62%; H, 6.05%; N, 18.90%; Cl, 23.26%.

Example 2 The procedure of Example 1 is repeated substituting 316 partsof N-(y-hydroxypropyl)-N,N-trimethyleneurea for the urea derivativethere used. N-(y-chloropropyl) N,N-trimethylene-urea is the productobtained. Another name for this compound isl-(y-chloropropyD-tetrahydro-pyrimidinone-Z.

Example 3 An 88 yield of l-(B-chloropropyl)-5-methyl-imidazolidinone-2is obtained by repeating the process of Example 1 substituting 316 partsof l-(fi-hydroxypropyD- S-methyl-imidazolidinone-Z for the ureaderivative therein used.

Example 4 (b) 1 y-chloropropyl) 5 methyl-imidazolidinone-2 I (fromV(g)).

'(c) 1-(4-chlorobutyl)-imidazolidinone-2 (from V(h)).

(d) 1-( IO-chlorodecyl)-imidazolidinone-2 (from V(j) The products ofparts (d) and (e) of Example 4 are 5 applied to the uppers of leatherboots and impart a lubricous feel and water-repellent finish thereon.

Example 6 A mixture of parts of 37% formaldehyde, 149 parts ofN-(p-chloroethyl)-N,N-ethyleneurea in 270 parts of water containing 1part of oxalic acid is applied to a rayon fabric, dried and then heatedto 300 F. for five minutes. The treated fabric has a crisp hand and ismarkedly improved in resistance to shrinkage.

It is to be understood that changes and variations may be made withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

I claim:

1. A compound having the formula:

l where A is an alkylene group having 2 to 3 carbon atoms of which atleast two extend in a chain between the adjoined N atoms, Z is analkylene group having 2 to 18 carbon atoms of which at least two extendin a chain between the N and X atoms, and X is a halogen selected fromthe group consisting of chlorine and bromine.

2. l-(fi-chloropropyl)-5-methyl-imidazolidinone-Z.

3. 1-(4-chlorobutyl)-imidazolidinone-2.

4. l-(B-chlorodecyl)-5-methyl-imidazolidinone-2.

5. l-(p-chloroethyl)-imidazolidinone-2.

6. l-(y-chloropropyl)-tetrahydro-pyrimidinone-2.

7. The method of making a compound as defined in claim 1 which comprisesreacting a thionyl halide of the formula SOX where X is a halogenselected from the group consisting of chlorine and bromine with a cycliccompound of the formula:

A HN NZOH Where A is an alkylene group having 2 to 3 carbon atoms ofwhich at least two extend in a chain between the adjoined N atoms, and Zis an alkylene group having 2 to 18 carbon atoms, the reaction beingeffected by mixing the thionyl halide with the cyclic compound in asolvent for the latter which is inert to the thionyl halide at atemperature in the range of about 30 to C.

8. The method as defined in claim 7 in which the solvent is chloroformand the reaction is effected at reflux.

9. The method as defined in claim 7 in which the solvent initiallypresent is chloroform and another solvent of higher boiling point isgradually added and the chloroform is distilled off by raising thetemperature gradually up to about 110 C.

10. The method as defined in claim 7 in which the solvent initiallypresent is chloroform, toluene is gradually added, and the chloroform isdistilled off by raising the temperature gradually up to about 110 C.

No references cited.

1. A COMPOUND HAVING THE FORMULA: